ES2641464T3 - Low toxicity solvent system for polyamideimide resins and solvent system manufacturing - Google Patents
Low toxicity solvent system for polyamideimide resins and solvent system manufacturing Download PDFInfo
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- ES2641464T3 ES2641464T3 ES12858583.3T ES12858583T ES2641464T3 ES 2641464 T3 ES2641464 T3 ES 2641464T3 ES 12858583 T ES12858583 T ES 12858583T ES 2641464 T3 ES2641464 T3 ES 2641464T3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
Un proceso para producir poliamidaimida que comprende hacer reaccionar un diisocianato con anhídrido trimelítico usando al menos un disolvente de dialquilamida aprótica, en el que el al menos un disolvente de dialquilamida aprótica es N-acetilmorfolina, N-formilmorfolina o N-propionil morfolina; en el que una relación del al menos un disolvente de dialquilamida aprótica a otros codisolventes del proceso es desde 19:1 hasta 1:1; y en el que los otros codisolventes del proceso se seleccionan de entre el grupo de agua, o-xileno, trietilamina, dimetiletanolamina, morfolina, N-metilmorfolina, acetona, trimetilamina, tripropilamina, dietilamina, diisopropilamina y caprolactamaA process for producing polyamidaimide comprising reacting a diisocyanate with trimellitic anhydride using at least one aprotic dialkylamide solvent, wherein the at least one aprotic dialkylamide solvent is N-acetylmorpholine, N-formylmorpholine or N-propionyl morpholine; wherein a ratio of the at least one aprotic dialkylamide solvent to other co-solvents in the process is from 19: 1 to 1: 1; and wherein the other co-solvents of the process are selected from the group of water, o-xylene, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, acetone, trimethylamine, tripropylamine, diethylamine, diisopropylamine and caprolactam
Description
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DESCRIPCIONDESCRIPTION
Sistema disolvente de baja toxicidad para resinas de poliamidaimida y fabricacion de sistemas disolventes Campo de la invencionLow toxicity solvent system for polyamideimide resins and solvent system manufacturing Field of the invention
Las realizaciones de la presente invencion se refieren al campo de los disolventes; mas particularmente, las realizaciones de la presente invencion se refieren a disolventes y su uso en la produccion de poliamidaimida.The embodiments of the present invention refer to the field of solvents; more particularly, the embodiments of the present invention relate to solvents and their use in the production of polyamideimide.
Antecedentes de la invencionBackground of the invention
Los polfmeros de poliamidaimida (PAI) se usan en muchas aplicaciones de recubrimiento de alto rendimiento debido a su excelente resistencia a la temperatura y alta resistencia. La via principal para sintetizar polfmeros de poliamidaimida en una forma que sea conveniente para la fabricacion de recubrimientos es haciendo reaccionar diisocianato, a menudo 4,4'-metileno difenildiisocianato (MDI) con antudrido trimelttico (TMA). En este proceso, los polfmeros PAI se sintetizan tfpicamente en disolventes aproticos polares tales como compuestos de N-metilamida que incluyen dimetilformamida, dimetilacetamida, N-etilpirrolidona (NMP), N-etilpirrolidona. Vease, por ejemplo, las Patentes de Estados Unidos Numero 2.421.021; 3.260.691; 3.471.444; 3.518.230; 3.817.926; y 3.847.878. El nivel de solidos de polfmero tfpico alcanzado en esta via sintetica es de 35-45 %, que se puede diluir ademas con diluyentes dependiendo de la aplicacion de recubrimiento de uso final.Polyamidaimide (PAI) polymers are used in many high-performance coating applications due to their excellent temperature resistance and high strength. The main route to synthesize polyamideimide polymers in a manner that is convenient for the manufacture of coatings is by reacting diisocyanate, often 4,4'-methylene diphenyldiisocyanate (MDI) with trimellitic antudide (TMA). In this process, PAI polymers are typically synthesized in polar aprotic solvents such as N-methylamide compounds including dimethylformamide, dimethylacetamide, N-ethylpyrrolidone (NMP), N-ethylpyrrolidone. See, for example, United States Patents Number 2,421,021; 3,260,691; 3,471,444; 3,518,230; 3,817,926; and 3,847,878. The level of typical polymer solids reached in this synthetic route is 35-45%, which can also be diluted with diluents depending on the end-use coating application.
Los disolventes alternativos tales como tetrahidrofurano, metil etil cetona, gamma-butirolactona o dimetilsulfoxido tienen inconvenientes tales como punto de ebullicion demasiado bajo para su uso como disolvente de reaccion, baja solubilidad del polfmero o pobre estabilidad de almacenamiento, que puede cambiar el rendimiento de aplicacion de la resina polimerica.Alternative solvents such as tetrahydrofuran, methyl ethyl ketone, gamma-butyrolactone or dimethylsulfoxide have disadvantages such as boiling point too low for use as a reaction solvent, low polymer solubility or poor storage stability, which can change the application performance of the polymeric resin.
Las Patentes de Estados Unidos Numero 4.950.700 y 5.095.070 recitan ejemplos de codisolventes de gamma- butirolactona con N-metilamida y dimetilol etileno urea como disolventes de sustitucion para sintetizar resina PAI. Sin embargo, la gamma-butirolactona tiene propiedades neurologicas que la someten a regulacion y no es adecuada para uso general en formulaciones. El dimetilol etileno urea no tiene estudios toxicologicos extensos realizados y contiene una funcionalidad N-metilamida sospechosa de impactos negativos en el medio ambiente y en la salud. Los nuevos disolventes, tales como los descritos en la Publicacion de Solicitud de Patente de Estados Unidos Numero 20100076223A1, por ejemplo, 3 metoxi-N, N-dimetil-propionamida, puede ser demasiado caro o no se han probado completamente para toxicidad a largo plazo.US Patent Nos. 4,950,700 and 5,095,070 recite examples of gamma-butyrolactone co-solvents with N-methylamide and dimethylol ethylene urea as substitution solvents for synthesizing PAI resin. However, gamma-butyrolactone has neurological properties that subject it to regulation and is not suitable for general use in formulations. Dimethylol ethylene urea has no extensive toxicological studies and contains an N-methylamide functionality suspected of negative impacts on the environment and health. The new solvents, such as those described in U.S. Patent Application Publication Number 20100076223A1, for example, 3 methoxy-N, N-dimethyl-propionamide, may be too expensive or have not been fully tested for long-term toxicity .
La patente de Estados Unidos 3790530 divulga un metodo para fabricar resinas de amida-imida, amidas aromaticas y resinas de poliamida aromatica.US Patent 3790530 discloses a method for manufacturing amide-imide resins, aromatic amides and aromatic polyamide resins.
La patente de Estados Unidos 3.843.587 divulga resinas de poliamida preparadas a partir de la reaccion de diisocianatos aromaticos con mezclas de acidos policarboxflicos y antudridos.US Patent 3,843,587 discloses polyamide resins prepared from the reaction of aromatic diisocyanates with mixtures of polycarboxylic acids and antisense.
La patente de Estados Unidos 4.003.947 divulga una composicion de recubrimiento y un metodo para recubrir sustratos con la misma.US Patent 4,003,947 discloses a coating composition and a method for coating substrates therewith.
La patente de Estados Unidos 4.098.775 divulga poliamidaimidas que se derivan de procedimientos convencionales a partir de compuestos de bis(fenilamina) 1,1 -cicloalipaticas particulares (o los diisocianatos correspondientes) y acido trimelftico (preferentemente a traves del cloruro de antudrido de acido).US Patent 4,098,775 discloses polyamidaimides that are derived from conventional procedures from particular bis (phenylamine) 1,1-cycloalipatic compounds (or the corresponding diisocyanates) and trimellophic acid (preferably through the acid antudide chloride ).
La patente de Estados Unidos 3.463.764 divulga un metodo para la produccion de polfmeros por la polimerizacion radical de monomeros en un disolvente.US Patent 3,463,764 discloses a method for the production of polymers by radical polymerization of monomers in a solvent.
La patente de Estados Unidos 3.939.109 divulga acidos poliamicos preparados a partir de dianhudrido 3,3,4,4- benzidrol tetracarboxflico.US Patent 3,939,109 discloses polyamic acids prepared from 3,3,4,4-benzidrol tetracarboxylic dianhydride.
La patente de Estados Unidos 2009/208868 divulga una composicion de resina fotosensible positiva y metodo para formar patron.US Patent 2009/208868 discloses a positive photosensitive resin composition and method to form a pattern.
La patente de Estados Unidos 5.756.647 divulga un proceso para la polimerizacion de lactama anionica activada.US Patent 5,756,647 discloses a process for the polymerization of activated anionic lactam.
La patente de Estados Unidos 4.408.032 divulga resinas de poliamidaimida modificadas y metodo para fabricar las mismas.US Patent 4,408,032 discloses modified polyamideimide resins and method of manufacturing them.
La patente de Estados Unidos 2005/043502 divulga una resina de poliamidaimida, metodo para producir la resina de poliamidaimida, composicion de resina poliamidaimida, material filmogeno y adhesivo para piezas electronicas.United States Patent 2005/043502 discloses a polyamideimide resin, method for producing polyamideimide resin, polyamideimide resin composition, filmogen material and adhesive for electronic parts.
Ademas, los disolventes proticos tales como el lactato de etilo y el propilenglicol no son adecuados para su usoIn addition, protic solvents such as ethyl lactate and propylene glycol are not suitable for use.
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como medio de reaccion PAI.as a means of PAI reaction.
En un nivel practico, estos disolventes conocidos en la tecnica, mientras que pueden ser utiles para la fabricacion de PAI o eficaces para otras reacciones sinteticas organicas, tambien se reconocen por tener problemas de toxicidad. Por lo tanto, es una ventaja producir poKmeros de poliamidaimida usando un metodo sintetico con un impacto mmimo en la salud y en la seguridad.On a practical level, these solvents known in the art, while they may be useful for the manufacture of EPI or effective for other organic synthetic reactions, are also recognized as having toxicity problems. Therefore, it is an advantage to produce polyamideimide polymers using a synthetic method with a minimal impact on health and safety.
Sumario de la invencionSummary of the invention
Se divulga un proceso para producir poliamidaimida. En una realizacion, el proceso comprende usar al menos un disolvente de dialquilamida aprotica.A process for producing polyamidaimide is disclosed. In one embodiment, the process comprises using at least one aprotic dialkylamide solvent.
Descripcion detallada de la presente invencionDetailed description of the present invention
La presente divulgacion proporciona un proceso y un producto de poliamidaimida obtenible mediante el proceso como se define en las reivindicaciones.The present disclosure provides a process and a polyamideimide product obtainable by the process as defined in the claims.
En un esfuerzo por lograr alternativas mas seguras, en particular, una via de smtesis libre de disolventes de N- metilamida usados habitualmente, son necesarios disolventes alternativos de menor toxicidad. Las acetamidas son de interes debido a su toxicidad relativamente baja y facil preparacion a partir de dialquilaminas disponibles industrialmente, con un largo historial de baja toxicidad cronica. En particular, las dialquilamidas son utiles. N- acetilmorfolina (NAM), que es un disolvente de baja toxicidad se ha descubierto ser adecuado para su uso en fabricacion de resinas de poliamidaimida. Otros disolventes utiles y de baja toxicidad son la dietilacetamida (DEAc), di-n-propilacetamida, N-formilmorfolina, diacetilpiperazina, N,N-di-isopropilacetamida (DIPAc), di-n-butilacetamida (DI-BAc), di-n-propilacetamida (DIPA) y N-propionil morfolina (NPM). Para lograr un proceso de menor toxicidad, ahora se ha descubierto que la smtesis de PAI puede conseguirse mediante el uso de disolventes de dialquilamida aprotica de la invencion, ya sean solos, en combinacion entre sf o con el uso de un codisolvente para proporcionar un sistema disolvente unico. El uso de una combinacion de disolventes puede requerirse, por ejemplo, para varias aplicaciones industriales de PAI, donde una viscosidad dentro de un intervalo espedfico se desea. Estos disolventes entonces pueden actuar tambien como diluyentes. Para lograr esto, se puede usar una combinacion de disolventes de dialquilamida para obtener la viscosidad deseada. Otros codisolventes preferentes de baja toxicidad que se pueden usar tanto para la smtesis de, o como diluyentes para disolucion de, resina PA1 son: el agua, o-xileno, trietilamina, dimetiletanolamina, morfolina, N-metilmorfolina, acetona, trimetilamina, tripropilamina, dietilamina, diisopropilamina y caprolactama.In an effort to achieve safer alternatives, in particular, a synthetic route free of commonly used N-methylamide solvents, alternative solvents of lower toxicity are necessary. Acetamides are of interest due to their relatively low toxicity and easy preparation from industrially available dialkylamines, with a long history of low chronic toxicity. In particular, dialkylamides are useful. N-acetylmorpholine (NAM), which is a low toxicity solvent has been found to be suitable for use in the manufacture of polyamideimide resins. Other useful and low toxic solvents are diethylacetamide (DEAc), di-n-propylacetamide, N-formylmorpholine, diacetylpiperazine, N, N-di-isopropylacetamide (DIPAc), di-n-butylacetamide (DI-BAc), di- n-propylacetamide (DIPA) and N-propionyl morpholine (NPM). To achieve a process of lower toxicity, it has now been discovered that the synthesis of EPI can be achieved through the use of aprotic dialkylamide solvents of the invention, either alone, in combination with each other or with the use of a cosolvent to provide a system unique solvent. The use of a combination of solvents may be required, for example, for several industrial applications of EPI, where a viscosity within a specific range is desired. These solvents can then also act as diluents. To achieve this, a combination of dialkylamide solvents can be used to obtain the desired viscosity. Other preferred low toxicity co-solvents that can be used both for the synthesis of, or as diluents for dissolution of, PA1 resin are: water, o-xylene, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, acetone, trimethylamine, tripropylamine, diethylamine, diisopropylamine and caprolactam.
Tambien se ha descubierto que una ventaja adicional de las realizaciones de la invencion es que, usando una o mas dialquilamidas aproticas en el proceso sintetico, una unica reaccion de dos pasos en crisol es posible.It has also been found that an additional advantage of the embodiments of the invention is that, using one or more aprotic dialkylamides in the synthetic process, a single two-step reaction in crucible is possible.
Ademas, el uso de los disolventes de la tecnica anterior para la smtesis de resina PAI, tal como N-metilamidas, se evita debido a la toxicidad de estos compuestos.In addition, the use of prior art solvents for PAI resin synthesis, such as N-methylamides, is avoided due to the toxicity of these compounds.
Espedficamente, las relaciones molares preferentes de dialquilamida aprotica a otros codisolventes de proceso son desde 19:1 a 1:1. Mas preferente es una relacion de desde 80:20 hasta 70:30. Mas preferente es una relacion de 78:22.Specifically, the preferred molar ratios of aprotic dialkylamide to other process cosolvents are from 19: 1 to 1: 1. More preferred is a ratio from 80:20 to 70:30. More preferred is a 78:22 ratio.
Ejemplos:Examples:
Ejemplo 1-metodo para sintetizar sistema codisolvente:En un matraz de 4 bocas de 1 l equipado con termometro, condensador y agitacion mecanica, anadir 200 g de dietilamina. Anadir 279,16 g de anhudrido acetico mientras se mantiene la temperatura por debajo de 55 °C. Esto se sigue por la adicion de 250,15 g de morfolina. La reaccion se calienta hasta ~130 °C hasta que se consuma el acido acetico (~8 h).La conversion se potencia por la destilacion de agua/exceso de morfolina.Example 1-method to synthesize co-solvent system: In a 4-mouth flask of 1 l equipped with thermometer, condenser and mechanical agitation, add 200 g of diethylamine. Add 279.16 g of acetic anhydride while maintaining the temperature below 55 ° C. This is followed by the addition of 250.15 g of morpholine. The reaction is heated to ~ 130 ° C until acetic acid is consumed (~ 8 h). The conversion is enhanced by the distillation of water / excess morpholine.
Ejemplo 2 (KM-1145): Carga de 51 g de N-acetilmorfolina (NAM), 0,85 g de caprolactama, 19,8 g de MDI, 15,65 g de TMA y calentar a 100 °C. En solucion a 96 °C, mantener 1,5 horas. La temperatura se redujo a 70 °C durante la noche, despues se calento a 130 °C durante 1,25 horas. Viscosidad demasiado alta; anadir 12,2 g de codisolvente NAM del Ejemplo 1.Example 2 (KM-1145): Load 51 g of N-acetylmorpholine (NAM), 0.85 g of caprolactam, 19.8 g of MDI, 15.65 g of TMA and heat to 100 ° C. In solution at 96 ° C, keep 1.5 hours. The temperature was reduced to 70 ° C overnight, then heated to 130 ° C for 1.25 hours. Viscosity too high; add 12.2 g of NAM cosolvent of Example 1.
% Solidos = 33,82 %, Viscosidad (DVII, 23 °C) = 63 Pa s (igual a 63.000 cps).% Solids = 33.82%, Viscosity (DVII, 23 ° C) = 63 Pa s (equal to 63,000 cps).
Ejemplo 3 (JES-3-29): Cargar 1,68 g de caprolactama, 31,49 g de TmA, 39,66 g de MDI y 102,12 g de codisolvente de NAM del Ejemplo 1 y calentar a 110 °C durante 1,5 horas. Calentar a 130 °C y supervisar la viscosidad hasta que sea >2 Pa s (igual a 2.000 cps) / 120 °C (~7 horas). Enfriar a <80 °C, anadir codisolvente NAM del Ejemplo 1 para mantener la agitacion. Anadir TEA manteniendo lentamente la temperatura por debajo de 90 °C. Mantener >60 °C durante 1 - 2 horas. Anadir agua para ajustar a ~28 % de solidos. Calentar y mantener a 85 °C y ajustar pH > 8 con TEA y agua segun se necesite para lograr homogeneidad.Example 3 (JES-3-29): Load 1.68 g of caprolactam, 31.49 g of TmA, 39.66 g of MDI and 102.12 g of NAM cosolvent of Example 1 and heat at 110 ° C for 1.5 hours Heat to 130 ° C and monitor viscosity until> 2 Pa s (equal to 2,000 cps) / 120 ° C (~ 7 hours). Cool to <80 ° C, add NAM cosolvent of Example 1 to maintain stirring. Add TEA slowly keeping the temperature below 90 ° C. Maintain> 60 ° C for 1 - 2 hours. Add water to adjust to ~ 28% solids. Heat and maintain at 85 ° C and adjust pH> 8 with ASD and water as needed to achieve homogeneity.
Ejemplo 4 (KM277): Un matraz de fondo redondo de 250 ml equipado con agitador mecanico, condensador y burbujeador de nitrogeno se cargo con: 57,6 g de n-acetilmorfolina, 18,9 g de o-xileno, 1,3 g de caprolactam, 29,7 g de diisocianato de difenilmetileno y 23,5 g de anhudrido trimelttico. La reaccion se calento a 90 °C duranteExample 4 (KM277): A 250 ml round bottom flask equipped with a mechanical stirrer, condenser and nitrogen bubbler was charged with: 57.6 g of n-acetylmorpholine, 18.9 g of o-xylene, 1.3 g of caprolactam, 29.7 g of diphenylmethylene diisocyanate and 23.5 g of trimellitic anhydride. The reaction was heated at 90 ° C for
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2 horas. La temperatura de reaccion se calento a 130 °C durante 5 horas y despues 14,7 g de acetilmorfolina y se anadio 3,68 g de o-xileno y el reactor se refrigero a temperatura ambiente. La viscosidad final fue de 13,834 Pa s (igual a 13.834 cps) a 23 °C usado un viscosfmetro DVII Brookfield.2 hours. The reaction temperature was heated at 130 ° C for 5 hours and then 14.7 g of acetylmorpholine and 3.68 g of o-xylene was added and the reactor was cooled to room temperature. The final viscosity was 13,834 Pa s (equal to 13,834 cps) at 23 ° C using a Brookfield DVII viscometer.
Ejemplo 5 (MP-2-11): Un matraz de fondo redondo de 250 ml equipado con agitador mecanico, condensador y burbujeador de nitrogeno se cargo con: 49 g de n-acetilmorfolina, 18,9 g de diethylacetamide, 1,3 g de o-xileno, 29,7 g de diisocianato de difenilmetileno y 23,6 g de anhndrido trimelttico. La reaccion se calento a 90 °C durante 2 horas. La temperatura de reaccion se calento entonces a 130 °C durante 3 horas y despues se anadio 3,74 g de n-acetilmorfolina y el reactor se refrigero a 60 °C. Entonces se anadieron 14,7 g en gotas, y el reactor se refrigero a temperatura ambiente. La viscosidad final fue de 3,076 Pa s (igual a 3.076 cps) a 23 °C usado un viscosfmetro DVlI Brookfield.Example 5 (MP-2-11): A 250 ml round bottom flask equipped with a mechanical stirrer, condenser and nitrogen bubbler was charged with: 49 g of n-acetylmorpholine, 18.9 g of diethylacetamide, 1.3 g of o-xylene, 29.7 g of diphenylmethylene diisocyanate and 23.6 g of trimellitic anhydride. The reaction was heated at 90 ° C for 2 hours. The reaction temperature was then heated at 130 ° C for 3 hours and then 3.74 g of n-acetylmorpholine was added and the reactor was cooled to 60 ° C. Then 14.7 g in drops were added, and the reactor was cooled to room temperature. The final viscosity was 3,076 Pa s (equal to 3,076 cps) at 23 ° C using a Brookfield DVlI viscometer.
Ejemplo 6 (KM38): Un matraz de fondo redondo de 500 ml equipado con agitador mecanico, condensador y burbujeador de nitrogeno se cargo con: 121 g de n-acetilmorfolina, 52,9 g de diisocianato de difenilmetileno y 40,92 g de anhndrido trimelttico. La reaccion se calento a 88 °C durante 3 horas. Despues, la temperatura de reaccion se calento a 120 °C hasta que la viscosidad templada alcanzo 1,680 Pa s (1680 cps) (2,5 horas) y despues se anadio 41.81 g de n-formilmorfolina y 41,81 g de o-xileno en la reaccion templada. El reactor se refrigero a temperatura ambiente. La viscosidad final fue 8,573 Pa s (8573 cps) a 23 °C usando un viscosfmetro DVII Brookfield.Example 6 (KM38): A 500 ml round bottom flask equipped with a mechanical stirrer, condenser and nitrogen bubbler was charged with: 121 g of n-acetylmorpholine, 52.9 g of diphenylmethylene diisocyanate and 40.92 g of anhydride Trimeltic. The reaction was heated at 88 ° C for 3 hours. Then, the reaction temperature was heated to 120 ° C until the warm viscosity reached 1,680 Pa s (1680 cps) (2.5 hours) and then 41.81 g of n-formylmorpholine and 41.81 g of o-xylene were added. In the temperate reaction. The reactor was cooled to room temperature. The final viscosity was 8,573 Pa s (8573 cps) at 23 ° C using a Brookfield DVII viscometer.
Ejemplo 7 Comparativo (JES-4-21): 50,27 g de diisocianato de difenilmetileno, 38,62 g de anfndrido trimelttico y 206,56 g de n-formilmorfolina se cargaron en un vaso de precipitados de 400 ml. La mezcla de la reaccion se calento a 80 °C hasta aproximadamente 1 equivalente de CO2, por perdida de peso, se evoluciono. La reaccion se calento, entonces, a 130 °C hasta que la viscosidad templada alcanzo 730 Pa s (730 cps) y despues se anadieron 41,51 g de n-formilmorfolina adicional para templar la reaccion. El reactor se refrigero a temperatura ambiente. El contenido de solidos final se analizo para que fuera 26,02 % y la viscosidad fue de 10,264 Pa s (igual a 10264 cps) (usando un viscosfmetro DVII Brookfield).Comparative Example 7 (JES-4-21): 50.27 g of diphenylmethylene diisocyanate, 38.62 g of trimellitic anhydride and 206.56 g of n-formylmorpholine were loaded into a 400 ml beaker. The reaction mixture was heated at 80 ° C to approximately 1 equivalent of CO2, due to weight loss, it evolved. The reaction was then heated to 130 ° C until the temperate viscosity reached 730 Pa s (730 cps) and then 41.51 g of additional n-formylmorpholine was added to quench the reaction. The reactor was cooled to room temperature. The final solids content was analyzed to be 26.02% and the viscosity was 10,264 Pa s (equal to 10264 cps) (using a Brookfield DVII viscometer).
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| US201161576247P | 2011-12-15 | 2011-12-15 | |
| US201161576247P | 2011-12-15 | ||
| PCT/US2012/070192 WO2013090933A1 (en) | 2011-12-15 | 2012-12-17 | Low toxicity solvent system for polyamideimide resins and solvent system manufacture |
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| ES2641464T3 true ES2641464T3 (en) | 2017-11-10 |
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| Country | Link |
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| US (1) | US9751986B2 (en) |
| EP (1) | EP2791208B1 (en) |
| JP (1) | JP6087373B2 (en) |
| CN (2) | CN108384004A (en) |
| ES (1) | ES2641464T3 (en) |
| IN (1) | IN2014DN05779A (en) |
| SG (1) | SG11201403244WA (en) |
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| US20200377724A1 (en) * | 2017-08-01 | 2020-12-03 | Hitachi Chemical Company, Ltd. | Polyamideimide resin composition and fluorine-containing coating material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200377724A1 (en) * | 2017-08-01 | 2020-12-03 | Hitachi Chemical Company, Ltd. | Polyamideimide resin composition and fluorine-containing coating material |
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| Publication number | Publication date |
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| CN104144968A (en) | 2014-11-12 |
| JP6087373B2 (en) | 2017-03-01 |
| US9751986B2 (en) | 2017-09-05 |
| WO2013090933A1 (en) | 2013-06-20 |
| EP2791208B1 (en) | 2017-09-06 |
| SG11201403244WA (en) | 2014-07-30 |
| EP2791208A4 (en) | 2015-07-22 |
| CN108384004A (en) | 2018-08-10 |
| JP2015522660A (en) | 2015-08-06 |
| IN2014DN05779A (en) | 2015-04-10 |
| US20160002408A1 (en) | 2016-01-07 |
| EP2791208A1 (en) | 2014-10-22 |
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